Manufacture of stannic chlorid.



APPLICATION FILED FEI3.5, 1908.

v111191111111 Mar. 11,1913.

Il 'l lll.

I Ona-14 e drous chlorid being allowed to drain awayA WILLIAM F. DOEBFLINGEB, 0F NEW YORK, N. Y., ASSIGNOR, BY-MESNE ASSIGNMENTS,"

TO' NIAGARA ALKALI COMIANY, A Y0912.1ORA'IION' OF NEW YORK. l Y

MANUFACTURE 0F STANNIC CHILORID.

'To all 'whom z't may'concem: Y

Be lity known that I,1WILL'1AM F. .Dome FLINGER, acitizenof the United States, ref siding at New York, in the county of Kmgs '5"and Stateof New York, hav'e invented cerv ta'in new and useful Improvements 1n the.l

Manufacture of Stannic Chlorid, of .which the following is a specification. In my improved process, anhydrous stan-` nic chlorid is producedby the action of dry chlorin gas,- in the presence-of stannic ,chlorid vapor,gupon metallic-tinpreferably at a tempera-ture of about 35 heat of reaction being dissipated by` coolingsurfacesnear the point of reaction .and the anhyas formed. This stannic chlorid, 'or part of it, I use 'to saturate' the entering chlorin gaswith stannic chlorid vapor for the purpose of removing the last trace of watery from the chlorin. The presence of water being ,y prejudiciah the use of stannic chlorid vapor as mentioned is desirable since, as I have found, it is difficult otherwise. to get the .chlorin thoroughly dry. -In fact, lI have found that chlorin, even after passing through a sulfuric acid drying tower,

A' usually contains enough moisture to interfere withft'he smooth course ofthe manufacture and often results in the formation 'of undesirable by-products. To saturate the chlorin with -t-he stannic chlorid vapor I prefer to pass vthe chlorin in inverse direction to astream of anhydrous stannic chlof may take rid, onvl the counter-current principle. This place in a part of the same appavratus, hereafter referred to as the absorber, in which the tin and the dry chlorin combine, but I prefer to employ for the purpose a separate apparatus.' This apparatus term the saturator, and in it the chlorin, passing over an extended surface of liquid stannic chlorid-towing in the opposite direc`v tion, becomes saturated with stannic chlorid vapor. With the latter such moisture as the chlorin may contain combines to form tri-hydrate, which drops to the bottom and may be melted and run oil from time -to -time. ridlowing from the absorber' and saturator The liquid anhydrous st-annic chlois yellow from dissolved chlorin, whichrmav 'Y be removed by digestion with metallictin, in practice very simply by allowing the chlorid'to How pastand in contact with the tin. If thechlorid is in mot-ion the action prodisagreeable to use,

or.` the formation of Patented Maa-rinata; i i

Y ceeds4 rapidly, but it is quiet .it'may smug in cont-act with -the tin for along tlme bef'`A fore the chlorin is entirely removed. It is preferableto have the l tin suspended in the.'`

lstream instead of lying on the bottom of.

the apparatus former tends to and complete.

etc.,- often results in below the stream, as the?. make the action more rapid I now have a clear, colorless,

-1 liquid anhydrous stannic chlorid, which may f be marketed assuch; but in this form it is' and .its use in preparf ing bichlorid solution' for weighting silk, 4

waste Vof the bichlorid, free acidv or basic salts in the bath' which injure the silk, etc.l Its,

transportation is also diicult and expensive.

I therefore in general prefer to convert it.

intosolid crystalline 'hydrate or a solutionI o f a hydrate producing. the hydrate, the combinationy of rid is very violent and may result inv local decomposition, injuring the product, even' when conducted with external cooling., This danger is obviated by my method of produc'-l ing solid from I place in a vessel walls a part of the the desired amount of hydrate, in the form of ice, and then run in the anhydrous bi-vv chlorid, .which may have been previously termined degree. -In general I pre er to and marketit in such form. In'l so 'i anhydrous stannic chlorid. provided with jacketed water necessary to form cooled. The amount of ice is regulated sol that the heat of reaction will not be studicient to raise the entire; mass above a, redev keep the temperature well .below 50 0.]

When the ice is all melting, vI lcirculate a cooling medium through the jacket and reduce the tempera-I ture to say 0 C., then I gradually add the rest of the ice, necessary to' form the desired quantity .of hydrate, atsuch rate; that the temperature never rises abovev the desired point. Near'the end of the addition I allow'. the' temperature to rise gradually above the melting l point'of the' hydrate, even aidingV the melting by' circulating warm fluid through -the jacketed walls 4 if, necessary.

AWhenthe hydrate is all melted, and fthe contents ofthe vessel' have become uniform throughout, I run the hydrate ofi' into molds to cool and set. It can then bemarketedin.. such form, or 'it can be ground and sold asmelted, -o'r Y'while it is .ico

crystalline powder, or dissolved in water and soldas an aqueous solution.

7 5; i the water and the anhydrous stannic chlo-py generally,

As a specific example of producing say pentahydrate, I place 60 lbs. of ice in a vessel with jacketed walls, and run in upon the ice 743.5 lbs. of anhydrous bichlorid, previously cooled to 0o C. During the addition I circulate brine in the jacket. at a teniperature of --10o is evolved, and the Atemperature has got to about Oo C., I gradually add 196.5 lbs. more ice, keeping the temperature down by the flow of cooling brine in the jacket. At the end I allow the temperature to rise to about 5 C. above the melting point of the hydrate, allow it to become uniform throughout, and then run ite-ff into molds to solidify. This specific case is given merely by way of example and as the preferred mode of operation, this part of the invention consisting, in admixing all or part of the water, necessary to form hydrate from anhydrous stannic Chlo-rid, in the formi lof ice, and dissipating more or less of the heat, evolved 'by the reaction, by means of the latent 'heat of fusion of the ice, thus avoiding overheating either local or general.

It will be understood, of course, that in practising my method any suitable apparatus may be employed. In the annexed drawing I have illustrated, somewhat diagrammatically, a simple and convenient appara tus for the purpose. Therein, l

Figure 1 is a side view part-ly in vertical section of the apparatus for producing the anhydrous stannic chlorid. Fig. 2 is a section of the vessel i'n which the stannic chlorid is converted into hydrate.

Referring nowr to the drawing, the pre ferred manner of practising my method is as follows: The chlorin, preferably' produced electrolytically, and by preference dried as thoroughly as possible, is delivered to the apparatus through a conduit 1, from which it passes to the saturator 2. The latter is divided into successive communicating compartments by partitions 3, 4E', those numbered 'leaving spaces at both top and bottom and those numbered 4 leaving spaces only at the bottom, as shown. The chlorin gas in flowing through the saturator to the` therefore given a tortu' f gas outlet pipe 5 is ous course, and in passing under partitions et is brought i. to close association with a stream of liquid anhydrous stannic chlorid entering the vessel from the pipe 6 and issuing therefrom through the pipe 7, and hence liowing in opposite direction to the current of chlorin The chlorin is thus saturated with the chlorid vapor which at once comloinesl with any moisturewhich may be mixed with the chlorin, forming solid trihydrate. The latter collects on the bottom of the saturator and may be removedfrom time to time in any convenient way. From the saturator or drier 2 the chlorin containing of course more or less chlorid vapor, is

C. TWhen no more heatl led through the pipe 5 to the bottom portion of the absorber S. an upwardly extending narrow chamber t) provided with a jacket 10. The space beinto compartments by horizontal partitions as shown. Each compartment has an inlet pipe 11 by which a' cooling medium, for example brine, may be admitted, and an outlet pipe 12 by which the cooling medium is discharged. The inlet pipes may all/be connected with the same source (not show n) of cooling fluid, but in order to regulate the flow through the compartments separately, forbetter regulation of the cooling elect, each inlet pipe is provided with its own valve, as shown. Similarly, all the outlet pipes 12 may discharge into a common receptacle, not shown, but each is preferably provided with a valve, as indicated. Suitably disposed inside'the chamber 9, for eX- ample extending longitudinally and cent-rally thereof, is a cooling pipe or cham# ber 13, supplied with cooling iuid by a valved supply pipe 14, which may be con- 13 the fluid issues through an out-let pipe 13. In the annular space thus provided in the chamber 9 is a mass of metallic tin, 17, as pure and as free from oxid as possible, supported above the bottom of the chamber on a transverse perforated partition 16. The dry chlorin admitted through the pipe 5 flows up through the tin, which is preferably divided into irregular masses to provide numerous interstices, and being brought into close association with the tin combines rapidly therewith. Anhydrous stannic chlorid is thus produced,' which, trickling down through the tin, collects in the bottom of the chamber 9 below the perforated partition 16, whence all or as much of it as desired is delivered to the saturator or drier 2 by the pipe ib'efore mentioned. During the reaction between the tin and the chlorin the heat produced is taken up, by the cool' ing medium in pipe 13, at a rate sufficient to keepvthe temperature in the absorber preferably at about at sufficiently low temperature, or by regulating the flow ofthe jacket, oit both, as will: bel readily understood. Ars the tin in the absorber is consumed, fresh'metal may be added from time to time, preferably by means of a hopper 9, constructed in any well known way to per* escape of vapor in anymaterial amount. Ihe process is thus made continuous. Instead of passing all the bichlorid from the absorber through the saturator, more or less tween the jacket and the chamber is divided f fluid through theA mit the introduction of charges without the The latter comprises nected with the same' source as the pipes .11.

charge into the same receptacle as the pipes ria 35 C. This temperature can readily be sel cured by having the cooling fluid delivered iso 1,o55,617 l' i ofthe liquidv may be delivered direct-ly to the finisher (hereafter described) by means of a pipe 6El leading thereto from the bottom of the chamber 9.

v As previously stated, the anhydrous chlorid flowing from the saturator 2 contains chlorin in solution. The dissolved chlorin can be removed in any convenient way, but I prefer to combine itwith tin and thus utilize it for the production of stannic chlorid. This can be done in a suit-able vessel 18, which for convenience may be termed the finisher. This vessel is divided into compartments by partitions 19, and into the first compartment the liquidanhydrous bichlorid from the saturator 2 is delivered by the pipe 7, which extends to a point near the bottom of the vessel 18. The upper part of each compartment is in communication with the next through pipes t20 extending chlorid vapor which may escape condensa 30. The vapor there combinesl wit-h the4 adjacent to the bottom of the finisher, as shown, so that the current of the chlorid is upward in each compartment. The chlorid, and hence also the chlorin dissolved in it, are thus brought into intimate association with loose masses of metallic tin suspended in the compartments in baskets 21, with the result that the dissolved chlorin combines With the tin, forming anhydrous stannic chlorid, which ows o with the rest through the outlet pipe 22 leading to a suitable storage reservoir, not shown. The

anhydrous stannic chlorid vapor in the absorber is conducted from the top lthereofthrough a pipe 23 to a suitable condenser 24, provided with an inlet A pipe 25 fora suitable cooling Huid and with an outlet pipe 26 for the discharge ofthe same. From the bottom of the condenser the stannic chlorid is led by' a pipe 27 tothe pipe 6, thence it isv delivered tothe finisher 18 .for'the re`v moval of dissolved chlorin." Any stannic tion is conducted through a pipe 28 to a suitable -washer 29, where it is brought into contact with water sprayed from a nozzle water to form hydrate, which goes into solution and .flows out through an outlet pipe` l31. If desired, the weak hydrate solution may be returned (by any suit-able means not shown) to the spray nozzle, and this procedure may bekept up `until the solution is a strong enough 'for eiicient utilization.

If desired, asuitable fan may be introduced at a convenient point, as at 32 in the pipe 29, to maintain the gas and vapor at an eiicient rate of flow through the apparatus. 'Y v As previously stated, the liquid anhydrous stann'ic chlorid, delivered from the finisher 18, may be marketed 'in such form, but it is preferable first to convert ityinto a hydrate, for example penta-hydratel* For this purpose I. provide a vessel'33, having-a.

being aided jacket-,34; a cooling medium from pipe 35, or a heating medium from pipe 36, being delivered thereto through a pipe 37 and discharged th-rou h an outlet pipe 38. The ice which is `use in making the hydrate is placed in the' vessel 33, andthe liquid anhydrous bichlorid is admitted throu h a pipe '39 extending to the bottom of t e vessel.

1s then run in through the pi e 39. During the addition of the bichlorld brine at a temperature of about -10 C. is passed around the vessel, and when no more heatl is evolved, and the temperature in t-he vessel has reached about 0 C., 196.5 lbs. more -ice is-added. Finally, when the reaction is completed, the temperature is allowed to 4rise to about 5 C. above the melting point' of the hydrate, the increase of temperature if necessary by introducingwarmer fluid into the jacket. The'melted .hydrate is then drawn olf through an outlet `pipe 40 into suitable molds in which the hy-y drate cools and solidifies..

The method herein described has been found in practice to yield highly satisfactory results, being economical to a marked degree. No deleterious by-products are formed, and the purity of the'bichlorid or lthe hydrate depends practically entirely -Iupon the purity of the tin and chlorin employed.

While this process has been described in detail with reference to the production of can be used i-n connection with the production ofvarous other substances, and the invention is limited only by the scope of the .appended claims. J

What I claim is: 1. In a process ofproducingstannic chlorid, passing chlorin overl liquid anhydrous stannic chlorid under conditions whereby -stannic chlorid, it is obvious that .,various.. modlfications can be made, and the process the moisture inthe chlorin will; combine with the stannic chlorid forming a speciically heavier hydrate which drops below the surface of the anhydrous liquid stan nic chlorid and is thus removed fromthe sphere of action, combining' the chlorin thus dried with tin to' produce stannic chlorid, and treating thechlorin gas entering the process with at least a part ofthe stannic chlorid thereby produce 2. In a. process of producing stannic chlcrid, passing chlorin over'liqui'd anhydrous stannic' chlorid, whereby moisture inv the chlorin will: be removed by combination Withv recaer? the vapor of the stannic chlorid; passing the densed from the exit gases and passing the chlorin thus dried, in contact with metallic mixture in contact with metallic tin, in tin, collecting lthe stannic chlorid thus tortuous course. 1

formed, and passing the same with the an- 6. A process of drying a gas which comf 5 hydrous stannic chlorid remaining from the prises passing the gas incontact with. a 70 step of'dr ing the chlorin, in contact with liquid of such a nature as to unite with the metallic tin to remove dissolved chlorin moisture present in said gas to produce `a therefrom by causing the vsame to combine solid product` which will separate from said with the tin to 4form an additional amount liquid, while maintaining'said liquid at a of stannicchlorid. temperature. below the melting point of said 75 3. In a process of producing stannic chlosolid product.

rid, passing chlorin over liquid anhy ous -7. A process of drying a v gas which comstannic chlorid under conditions .whereby prises passing the. as in a tortuous path in moisture in the chlorin will combine with contact at a plurallty of points-of said path the stannic chlorid and form a specifically with a liquid of' such a'nature as to unite 8'0 heavier hydrate vwhich drops below the surwith the moisture present in said gas to proface of the anhydrous liquid stannic chloduce a solid product whichwill separate ridandis'thus removed from the sphere of from said liquid,` while maintaining said action, passing the chlorin gas thusl dried liquid at atemperature below the meltinginto contact with metallic tin, collecting the point of said solid product. 35

j stannic chlorid' thus formed "and, bringing 8. A process of drying a gas which comapart of the -sarne into contactwith the 'prises passing the gas 1n Contact with'an chlorin gas entering the process, and bringanhydrous liquid of such a nature as to unite ing another part thereof into contact with with vthemoisture present insaid gas4 to metallic tin to remove dissolved chlorin 'by produce a solid product which will separate 9o permitting the same tov combine withalth from said liquid, while maintaining said to form an additionalv aroountof's vliquid at a temperature below the melting chlorid. y f point of said solid product.

. .4.' In the manufacture of stannic chlorid, 9. A process of drying a gas which com-v the method of -drying chlorin gas, which p-rises passing the gas in' contact with the 95 comprises passing the chlorin gas over liqsurface of a flowing liquid of such a nature uid anhydrous stannic chlorid, at temperaas to unite with the moisture present in said .,ture below 80 C.,fwhereby the moist-ure in gas to produce a. product which will sepathe gas unites with the anhydrous stannic rate from said liquid. chloridv to produce the specifically heavier 10. A process of drying a' gas which com- 100 hydrate which drops below the lsurI'ace of prises passing the gas lin contact with a the. anhydrous stannic Chlo-rid, and is therecounter current of a constantly renewed by removedl from the sphere o -action. liquid of such a nature as to unite with the 5. A process of making stannic chlorid moisture present in said gas to produce a 40 .which comprises passing chlorin gas in a product which will separate from said 105 tortuous pathovery the surface of a owing liquid. body of anhydrous stannic chlorid, at a .11. A process-of drying a gas which comtemperature below the melting point of hyprises passing the gas in contact with anhydrated stannic chlorid whereby 'the moisture drous stannic chlorid under temperature of the gas combines with the stannic chloconditions favorable to the formation and 110 rid and produces the speciiically heavier Separation of hydrated stannic chlorid hydrated stannic chlorid, which drops befrom the anhydrous stannic chlori'd.

' low the surface and out of contact with the .12. A process otdrying a gas which comv chlorin as; passing said dried as in conprises passing the gas in contact vwith antactl wit a body of metallic tin, and re'. .hydrous stannic chlorid under temperature 115 moving the heat of reaction from the inconditions favorableto the formation of terior and independently from the exterior .hydrated stannic ychlorid and to the precipiof said body of tin; drawing 0H one portation thereof to below the surface of the tion of the liquid stannic chlorid and passanhydrous stannic chlorid. ing the. same in Contact with vthe chlcrin 13.1A process of drying chlorin gas which 120 gas entering. the process; drawing ed ancomprises passing the gas in a tortuous path other portion of the liquid stannic chlorid in contact at a plurality of points of said x roduced; coolingy ythe gases and va ors path with the surface of owing anhydrous rom the step of reacting on tin with c lostannic chlorid under temperature condirin, to condense atleast a part of the stannic tions favorable to the formation of hydrated 125 chlorid contained therein; uniting' the anstannic chlorid and to the precipitation n hydrous stannic chlorid remaining from the thereof to below the surface of the anhystep of treat-in the chlorin gas with standrous stannic chlorid.

ni'c chlorid, wlth `that portion drawn off 14. A process oitreating a gaseous mixfrom the reaction vessel, and that con- -ture which comprises passing the gas in con-*13o tact with a liquid of such a nature as to unite with a normally liquid constituent of the gaseous mixture to produce a solid product which will separate from said liquid, While maintaining said liquid at a temperature below the melting point of said solid product. I v

15. A process of removing a.v particular constituent from a gaseous mixture which comprises passing the gaseous mixture in contact with an anhydrous liquid of such a nature as to unite with a constituent of the gaseous mixture to produce a solid product which will automatically separate from said liquid, While maintaining said liquid at a temperature below the melting point of said solid product.

16. A process of treat-ing a gaseous mixture which comprises passing the gas in contact with a. liquid of such a nature as to unite with a constituent of the gaseous mixture to produce a product which will separate from said liquid thereafter drawing off the unacted upon liquid and leaving the separated solid, melting the latter and drawing olf the same.

17. A process of treating a gaseous mixture which comprises passing the same in a tortuous path in contact at a plurality of points of said path With the surface of a flowing body of a liquid of such a nature as to unite with a normally liquid constituent of said gaseous mixture to produce a solid product which will be of greater specic gravity than said liquid and will settle to the bottom thereof; and thereafter drawof the separated stannic chlorid with the i chlorin gas entering the process and removing the unacted upon portion after treatment With said gas, and passing all of the anhydrous stannic chlorid in contact with metallic tin to remove dissolved chlorin therefrom. l

19. A process of removing vapors of chlorid of a metal from a gaseous body containing the same which comprises cooling the gaseous body sufficiently to cause condensation of a. part of said vapors, and thereafter washing the gaseous body repeatedly with the same volume of liquid.

20. A process of removing vapors of stannic chlorid from a gaseous body which comprises cooling the gaseous body suliciently to cause condensation of a part of said vapors, and thereafter Washing the gaseous body repeatedly with the same volume of liquid.

i 'WILLIAM F. DOERFLINGER.

Witnesses:

EDWARD MALONE, J oHN P. WILLIAMS. 

